Delocalized lithium ion flux by solid-state electrolyte composites coupled with 3d porous nanostructures for highly stable lithium metal batteries

Abstract

A lithium metal anode that reduces formation of lithium dendrites includes a porous carbon nanotube (CNT) electrode, a solid-state electrolyte (SE) composite layer disposed on the porous CNT electrode, and a polypropylene (PP) separator layer disposed on the SE composite layer. The SE composite layer induces uniform lithium growth, suppressing dendrite growth. The suppression of dendrite growth improves performance lithium-based designs and enables improved capacity retention.

1 . An electrode comprising:
 a porous carbon nanotube (CNT) electrode;   a solid-state electrolyte (SE) composite layer disposed on the porous CNT electrode; and   a polypropylene (PP) separator layer disposed on the SE composite layer.   
     
     
         2 . The electrode of  claim 1 , wherein the SE composite layer comprises Li 6.4 La 3 Zr 1.4  Ta 0.6 O 12  (LLZTO) and poly(vinylidene fluoride-co-hexafluoropropylene (PVDF-HFP). 
     
     
         3 . The electrode of  claim 2 , wherein the LLZTO comprises about 40-99 wt. % of the SE composite layer. 
     
     
         4 . The electrode of  claim 1 , wherein the SE composite layer comprises one or more of LLZTO, Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3  (LATP), Li 6 PS 5 Cl (Argyrodite), or Li 10 GeP 2 S 12  (LGPS). 
     
     
         5 . The electrode of  claim 4 , wherein the SE composite layer further comprises one or more of poly(ethylene oxide) (PEO), polyimide (PI), polyacrylonitrile (PAN), or poly(vinylidene fluoride-co-hexafluoropropylene (PVDF-HFP). 
     
     
         6 . The electrode of  claim 1 , wherein the porous CNT electrode comprises carboxyl functional groups. 
     
     
         7 . The electrode of  claim 1 , wherein the porous CNT electrode comprises polyvinylidene fluoride. 
     
     
         8 . A solid-state anode-free Li metal battery comprising:
 a separator composite layer; and   an elastic porous layer configured to change volume when the battery undergoes a charge or discharge process.   
     
     
         9 . The battery of  claim 8 , wherein the separator composite layer comprises SE. 
     
     
         10 . The battery of  claim 9 , wherein the SE comprises one or more of LLZTO, LATP, Argyrodite, or LGPS 
     
     
         11 . The battery of  claim 10 , wherein the SE further comprises one or more of PEO, PI, PAN, or PVDF-HFP. 
     
     
         12 . The battery of  claim 8 , wherein the elastic porous layer comprises a CNT sponge. 
     
     
         13 . The battery of  claim 12 , wherein the elastic porous layer further comprise an artificial solid electrolyte interphase (SEI) layer. 
     
     
         14 . The battery of  claim 13 , wherein the SEI layer comprises one or more of Li 13 In 3 , LiZn, Li 3 Bi, or Li 3 As. 
     
     
         15 . A method of making an anode, the method comprising:
 applying an SE composite layer to a porous CNT electrode while the SE composite is in an uncured state; and   applying a PP separator on top of the SE composite.   
     
     
         16 . The method of  claim 15 , wherein the SE composite layer comprises LLZTO and PVDF-HFP. 
     
     
         17 . The method of  claim 16 , wherein the LZTO comprises about 40-60 wt. % of the SE composite layer. 
     
     
         18 . The method of  claim 15 , wherein the porous CNT electrode comprises polyvinylidene fluoride. 
     
     
         19 . The method of  claim 15 , wherein the SE composite layer further comprises one or more of poly(ethylene oxide) (PEO), polyimide (PI), polyacrylonitrile (PAN), or poly(vinylidene fluoride-co-hexafluoropropylene (PVDF-HFP). 
     
     
         20 . The method of  claim 15 , further comprising incorporating the anode into a battery.